This invention relates to multicolor organic light emitting devices and more particularly to such devices for use in flat panel electronic displays.
The electronic display is an indispensable way in modern society to deliver information and is utilized in television sets, computer terminals and in a host of other applications. No other medium offers its speed, versatility and interactivity. Known display technologies include plasma displays, light emitting diodes (LEDs), thin film electroluminescent displays, and so forth.
The primary non-emissive technology makes use of the electro optic properties of a class of organic molecules known as liquid crystals (LCs) or liquid crystal displays (LCDs). LCDs operate fairly reliably but have relatively low contrast and resolution, and require high power backlighting. Active matrix displays employ an array of transistors, each capable of activating a single LC pixel. There is no doubt that the technology concerning flat panel displays is of a significant concern and progress is continuously being made. See an article entitled xe2x80x9cFlat Panel Displaysxe2x80x9d, Scientific American, March 1993, pgs. 90-97 by S. W. Depp and W. E. Howard. In that article, it is indicated that by 1995 flat panel displays alone are expected to form a market of between 4 and 5 billion dollars. Desirable factors for any display technology is the ability to provide a high resolution full color display at good light level and at competitive pricing.
Color displays operate with the three primary colors red (R), green (G) and blue (B). There has been considerable progress in demonstrating red, green and blue light emitting devices (LEDs) using organic thin film materials. These thin film materials are deposited under high vacuum conditions. Such techniques have been developed in numerous places; throughout the world and this technology is being worked on in many research facilities.
Presently, the most favored high efficiency organic emissive structure is referred to as the double heterostructure LED which is shown in FIG. 1A and designated as prior art. This structure is very similar to conventional, inorganic LED""s using materials as GaAs or InP.
In the device shown in FIG. 1A, a support layer of glass 10 is coated by a thin layer of Indium Tin Oxide (ITO) 11, where layers 10 and 11 form the substrate. Next, a thin (100-500 xc3x85) organic, predominantly hole transporting layer (HTL) 12 is deposited on the ITO layer 11. Deposited on the surface of HTL layer 12 is a thin (typically, 50 xc3x85-100 xc3x85) emission layer (EL) 13. If the layers are too thin there may be lack of continuity in the film, and thicker films tend to have a high internal resistance requiring higher power operation. Emissive layer (EL) 13 provides the recombination site for electrons injected from a 100-500 xc3x85 thick electron transporting layer 14 (ETL) with holes from the HTL layer 12. The ETL material is characterized by its considerably higher electron than hole mobility. Examples of prior art ETL, EL and HTL materials are disclosed in U.S. Pat. No. 5,294,870 entitled xe2x80x9cOrganic Electroluminescent MultiColor Image Display Devicexe2x80x9d, issued on Mar. 15, 1994 to Tang et al.
Often, the EL layer 13 is doped with a highly fluorescent dye to tune color and increase the electroluminescent efficiency of the LED. The device as shown in FIG. 1A is completed by depositing metal contacts 15, 16 and top electrode 17. Contacts 15 and 16 are typically fabricated from indium or Ti/Pt/Au. Electrode 17 is often a dual layer structure consisting of an alloy such as Mg/Ag 17xe2x80x2 directly contacting the organic ETL layer 14, and a thick, high work function metal layer 17xe2x80x3 such as gold (Au) or silver (Ag) on the Mg/Ag. The thick metal 17xe2x80x3 is opaque. When proper bias voltage is applied between top electrode 17 and contacts 15 and 16, light emission occurs through the glass substrate 10. An LED device of FIG. 1A typically has luminescent external quantum efficiencies of from 0.05 percent to 4 percent depending on the color of emission and its structure.
Another known organic emissive structure referred as a single heterostructure is shown in FIG. 1B and designated as prior art. The difference in this structure relative to that of FIG. 1A, is that the EL layer 13 serves also as an ETL layer, eliminating the ETL layer 14 of FIG. 1A. However, the device of FIG. 1B, for efficient operation, must incorporate an EL layer 13 having good electron transport capability, otherwise a separate ETL layer 14 must be included as shown for the device of FIG. 1A.
Presently, the highest efficiencies have been observed in green LED""s. Furthermore, drive voltages of 3 to 10 volts have been achieved. These early and very promising demonstrations have used amorphous or highly polycrystalline organic layers. These structures undoubtedly limit the charge carrier mobility across the film which, in turn, limits current and increases drive voltage. Migration and growth of crystallites arising from the polycrystalline state is a pronounced failure mode of such devices. Electrode contact degradation is also a pronounced failure mechanism.
Yet another known LED device is shown in FIG. 1C, illustrating a typical cross sectional view of a single layer (polymer) LED. As shown, the device includes a glass support layer 1, coated by a thin ITO layer 3, for forming the base substrate. A thin organic layer 5 of spin-coated polymer, for example, is formed over ITO layer 3, and provides all of the functions of the HTL, ETL, and EL layers of the previously described devices. A metal electrode layer 6 is formed over organic layer 5. The metal is typically Mg, Ca, or other conventionally used metals.
An example of a multicolor electroluminescent image display device employing organic compounds for light emitting pixels is disclosed in Tang et al., U.S. Pat. No. 5,294,870. This patent discloses a plurality of light emitting pixels which contain an organic medium for emitting blue light in blue-emitting subpixel regions. Fluorescent media are laterally spaced from the blue-emitting subpixel region. The fluorescent media absorb light emitted by the organic medium and emit red and green light in different subpixel regions. The use of materials doped with fluorescent dyes to emit green or red on absorption of blue light from the blue subpixel region is less efficient than direct formation via green or red LED""s. The reason is that the efficiency will be the product of (quantum efficiency for EL)*(quantum efficiency for fluorescence)*(1-transmittance). Thus a drawback of this display is that different laterally spaced subpixel regions are required for each color emitted.
The present invention is generally directed to a multicolor organic light emitting device and structures containing the same employing an emission layer containing a select group of emitting compounds selected for the transmission of desirable primary colors. The emission layer can optionally contain a matrix formed from host compounds which facilitate the transportation of electrons to the emitting compound.
In one embodiment of the present invention there is provided a multicolor light emitting device (LED) structure, comprising:
a plurality of at least a first and a second light emitting organic device (LED) stacked one upon the other, to form a layered structure, with each LED separated one from the other by a transparent conductive layer to enable each device to receive a separate bias potential to emit light through the stack, at least one of said LED""s comprising an emission layer, said emission layer comprising at least one of
a) a trivalent metal complex having the formula: 
xe2x80x83wherein M is a trivalent metal ion; Q is at least one fused ring, at least one of said fused rings containing at least one nitrogen atom; and L is a ligand selected from the group consisting of picolylmethylketone; substituted and unsubstituted salicylaldehyde; a group of the formula R1(O)COxe2x80x94 wherein R1 is selected from the group consisting of hydrogen, an alkyl group, an aryl group, and a heterocyclic group, each of which may be substituted with at least one substituent selected from the group consisting of aryl, halogen, cyano and alkoxy; halogen; a group of the formula R1Oxe2x80x94 wherein R1 is as defined above; bistriphenyl siloxides; and quinolates and derivatives thereof; p is 1 or 2 and t is 1 or 2 where p does not equal t; and
b) a trivalent metal bridged complex having the formula: 
xe2x80x83wherein M and Q are defined as above.
In a preferred form of the invention, the multicolor light emitting device (LED) comprises:
a plurality of at least a first and a second light emitting organic device (LED) stacked one upon the other, to form a layered structure, with each LED separated one from the other by a transparent conductive layer to enable each device to receive a separate bias potential to operate to emit light through the stack, at least one of said LED""s comprising an emission layer containing
a) a trivalent metal quinolate complex selected from the group consisting of a compound of the following formulas: 
xe2x80x83wherein R is selected from the group consisting of hydrogen, an alkyl group, an aryl group, and a heterocyclic group, each of which may be substituted with at least one substituent selected from the group consisting of aryl, halogen, cyano and alkoxy; M is a trivalent metal ion; L is a ligand selected from the group consisting of picolylmethylketone; substituted and unsubstituted salicylaldehyde; a group of the formula R1(O)COxe2x80x94 wherein R1 is selected from the group consisting of hydrogen, an alkyl group, an aryl group, and a heterocyclic group, each of which may be substituted with at least one substituent selected from the group consisting of aryl, halogen, cyano and alkoxy; halogen; a group of the formula R1Oxe2x80x94 wherein R1 is as defined above; bistriphenyl siloxides; and quinolates and derivatives thereof; A is an aryl group or a nitrogen containing heterocyclic group fused to the existing fused ring structure; n1 and n2 are independently 0, 1 or 2 and m1 and m2 are independently 1, 2, 3 or 4, and
b) a trivalent metal bridged quinolate complex of the following formulas: 
xe2x80x83wherein R, M, A, n1, n2, m1 and m2 are as defined above.
In another aspect of the present invention, the multicolor light emitting device (LED) structure comprises:
a plurality of at least a first and a second light emitting organic device (LED) stacked one upon the other, to form a layered structure, with each LED separated one from the other by a transparent conductive layer to enable each device to receive a separate bias potential to emit light through the stack, at least one of said LED""s comprising an emission layer, said LED""s comprising an emission layer, said emission layer comprising at least one of
a) a trivalent metal quinolate complex having the following formula: 
xe2x80x83wherein R is selected from the group consisting of hydrogen, an alkyl group, an aryl group, and a heterocyclic group, each of which may be substituted with at least one substituent selected from the group consisting of aryl, halogen, cyano and alkoxy; M is a trivalent metal ion; L is a ligand selected from the group consisting of picolylmethylketone; substituted and unsubstituted salicylaldehyde; a group of the formula R1(O)COxe2x80x94 wherein R1 is selected from the group consisting of hydrogen, an alkyl group, an aryl group, and a heterocyclic group, each of which may be substituted with at least one substituent selected from the group consisting of aryl, halogen, cyano and alkoxy; halogen; a group of the formula R1Oxe2x80x94 wherein R1 is as defined above; bistriphenyl siloxides and quinolates and derivatives thereof; and
b) a trivalent metal bridged quinolate complex of the following formulas: 
xe2x80x83wherein R and M are as defined above, with the proviso that each R can not be hydrogen at the same time.
The multicolor organic light emitting devices of the present invention may optionally contain host compounds which facilitate the carrying of electrons to the emitting compounds to initiate light emission.
The preferred host compounds are set forth below: 
wherein M for compounds represented by formulas (a) and (b) is a +3 metal while M1 for compounds represented by formulas (c) and (d) is a +2 metal; and R1 through R5 are each independently selected from the group consisting of hydrogen, alkyl and aryl.